The Valmalenco area (central Alps, northern Italy) is an excellent case study for naturally occurring asbestos (NOA) because of the huge outcrops of serpentinites and widespread quarrying and mining activities. Extensive sampling of rocks, soils, stream sediments, and airborne asbestos has been in progress since 2004. The combined use of scanning electron microscopy and transmission electron microscopy has proven to be effective for the correct discrimination between asbestiform and non-asbestiform mineralogical varieties (but falling into the World Health Organization fiber definition), whereas phase contrast microscopy has not proven suitable because of the very small size of fibrils after strong mechanical fragmentation. The quantitative analysis of “massive” samples (rocks, soils, and sediments) requires accurate and representative sampling as well as specific counting and discrimination criteria to determine NOA. Over a decade of experience has allowed us to identify critical issues and adopt effective preventive measures.